CN111039863B - Preparation method of rubber antioxidant TMQ - Google Patents
Preparation method of rubber antioxidant TMQ Download PDFInfo
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- CN111039863B CN111039863B CN201811189755.5A CN201811189755A CN111039863B CN 111039863 B CN111039863 B CN 111039863B CN 201811189755 A CN201811189755 A CN 201811189755A CN 111039863 B CN111039863 B CN 111039863B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3437—Six-membered rings condensed with carbocyclic rings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a rubber antioxidant TMQ. The method is mainly characterized in that a graphene oxide-based catalyst, namely a non-covalent modified product of organic protonic acid and graphene oxide, is used as the catalyst to prepare the TMQ. The graphene oxide-based catalyst is simple to prepare and has a good catalytic effect; the catalytic action of the graphene oxide-based catalyst can prevent a large amount of acid liquor from being used in the preparation of TMQ, so that the problems of equipment corrosion, alkali liquor neutralization, high three-waste treatment cost and the like are solved.
Description
Technical Field
The invention belongs to the field of rubber auxiliaries, and particularly relates to a preparation method of a rubber antioxidant TMQ, in particular to a preparation method of TMQ under the catalysis of a graphene oxide-based catalyst.
Background
The anti-aging agent TMQ (also known as anti-aging agent RD) belongs to ketoamine anti-aging agents, and the main component of the anti-aging agent is a di-tri-tetra-polymer of 2, 4-trimethyl-1, 2-dihydroquinoline, which is one of the rubber anti-aging agents with the largest market demand at home and abroad. At present, the preparation of TMQ in China can be divided into a "one-step method" and a "two-step method", wherein the "one-step method" is generally prepared by using aniline and acetone as raw materials and performing a series of steps of salt formation, condensation, polymerization, neutralization, distillation and the like under the catalysis of an acid catalyst, particularly hydrochloric acid. Therefore, the preparation of the anti-aging agent TMQ often faces the problems of serious equipment corrosion, huge consumption of alkaline water, high three-waste treatment cost and the like. In order to overcome the technical defects, a novel catalytic material is sought, and the environment-friendly preparation of TMQ is of great significance in reducing the consumption of hydrochloric acid and further reducing the generation of wastewater.
Besides hydrochloric acid, organic protonic acids such as p-toluenesulfonic acid, benzenesulfonic acid, phenolsulfonic acid and the like can also be used as catalysts of the anti-aging agent TMQ; the direct use of organic protonic acid catalyst also faces the problems of large amount of alkali liquor neutralization and huge amount of waste water, so we consider that a catalyst carrier which can stably combine the organic protonic acid and provide necessary reaction sites for the synthesis reaction needs to be sought. The graphene oxide is a carbon nano two-dimensional material with a single atomic layer, the single-layer thickness of the graphene oxide is only 0.335 nm, and the theoretical specific surface area is 2630 m 2 (iv) g. Graphene oxide is one of important derivatives of graphene, and a large number of oxygen-containing functional groups, such as hydroxyl (-OH), carboxyl (-COOH), carbonyl (C = O), epoxy (-O-), and the like, are introduced into the surface and the edge of graphene. On one hand, the graphene oxide retains part of the original delocalized pi conjugated structure of the graphene and provides a certain affinity for organic matters containing benzene rings, aromatic rings and heterocyclic structures; on the other hand, the oxygen-containing functional group of the graphene oxide provides a large number of affinity sites for various valence bond actions, and other functional groups can be introduced by modifying the sheet layer of the graphene oxide, so that a new composite material is formed to meet special technical requirements. Due to the characteristics, the graphene oxide has a very wide application prospect in the aspect of developing a catalyst carrier. In addition, graphene oxide has various modification modes such as covalent modification, non-covalent modification, nitrogen doping and metal particle deposition, and the non-covalent modification mode is easy to introduce a large number of functional groups into graphene oxide sheets, and has the advantages of remaining the complete sheet structure of graphene oxide, being simple and convenient to prepare and the like, so that the preparation method of the TMQ (tetramethylammonium hydroxide) by combining the organic protonic acid with the graphene oxide in a non-covalent modification mode and utilizing the non-covalent modification product of the graphene oxideThe catalyst is prepared, and a novel environment-friendly preparation method is provided.
Disclosure of Invention
The invention aims to provide a preparation method of a rubber antioxidant TMQ. The method uses aniline and acetone as raw materials, and the catalyst is prepared by the catalysis of a graphene oxide-based catalyst.
In order to achieve the purpose, the preparation method provided by the invention is realized by the following steps:
adding raw materials of aniline, acetone and a graphene oxide-based catalyst into a solvent, mixing, heating to a reaction temperature, reacting for a period of time, and distilling to remove the solvent to obtain the rubber antioxidant TMQ.
In the method, the reaction temperature for preparing the rubber antioxidant TMQ is 90-180 ℃, and the reaction time is 1-20 hours.
In the method, the weight ratio of aniline to acetone is 1:1 to 10, wherein the weight ratio of the graphene oxide-based catalyst to the aniline is 0.0005 to 0.5:1.
in the method, the graphene oxide-based catalyst is a non-covalent modified product of graphene oxide and organic protonic acid, and the preparation method comprises the following steps:
and (2) completely dispersing graphene oxide solid in a solvent, dissolving organic protonic acid in a graphene oxide system, stirring, washing with the solvent and deionized water, and freeze-drying a product to obtain a non-covalent modified product of graphene oxide and organic protonic acid.
Further, the solvent refers to a solvent that can completely disperse the graphene oxide and completely dissolve the organic acid compound at the same time, and includes, but is not limited to, water, methanol, ethanol, dioxymethane, chloroform, acetone, acetonitrile, ethyl acetate, N-dimethylformamide, and dimethylsulfoxide.
Further, the dispersion means ultrasonic or agitation dispersion.
Further, the organic protonic acid includes, but is not limited to, p-toluenesulfonic acid, benzenesulfonic acid, phenolsulfonic acid, oxalic acid, tartaric acid, citric acid, malic acid, lactic acid.
Further, the stirring time is 0 to 72 hours.
Further, the washing manner may be centrifugal washing and dialysis.
The invention has the advantages of
In the preparation process of the rubber antioxidant TMQ, on one hand, the use of a strong acid catalyst is avoided, and the processes of liquid alkali neutralization and water diversion are omitted, so that the generation of waste water is reduced; on the other hand, the organic protonic acid and the graphene oxide lamella are combined through non-covalent action, the modification method is simple, the product not only provides a catalytic active substance necessary for preparing TMQ, but also reserves the structure and the surface area of the graphene oxide lamella and provides sufficient reaction sites, and therefore, the catalyst has good catalytic activity.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not delimit the invention.
Example 1
Preparation of graphene oxide-based catalyst:
weighing 20 g of graphene oxide, and placing the graphene oxide in 4000 g of ethanol for thorough dispersion by ultrasonic waves. 30 g of p-toluenesulfonic acid is weighed, dissolved in 300 g of ethanol, added into a graphene oxide system and stirred for 48 hours. And after modification, washing and centrifuging by using ethanol and deionized water respectively to remove free p-toluenesulfonic acid, and freeze-drying a product to obtain a p-toluenesulfonic acid non-covalent modified product of graphene oxide for later use.
Preparing a rubber antioxidant TMQ:
to 500 g of toluene were added 10 g of the non-covalently modified product of graphene oxide-p-toluenesulfonic acid, 93 g of aniline and 928 g of acetone, and reacted at 160 ℃ for 15 h. And after the reaction is finished, separating liquid, removing the water phase and the p-toluenesulfonic acid non-covalent modified product of the graphene oxide, and then distilling to remove the organic solvent to obtain the product, namely the rubber antioxidant TMQ.
Example 2
Preparation of graphene oxide-based catalyst:
weighing 20 g of graphene oxide, and placing the graphene oxide in 4000 g of methanol for thorough dispersion by ultrasonic. 30 g of phenolsulfonic acid is weighed out and dissolved in 200 g of methanol, and added into a graphene oxide system, and then stirred for 72 hours. And after modification, washing and centrifuging by using methanol and deionized water respectively to remove free phenolsulfonic acid, and then freeze-drying the product to obtain a phenolsulfonic acid non-covalent modified product of graphene oxide for later use.
Preparing a rubber antioxidant TMQ:
to 500 g of toluene were added 10 g of the non-covalently modified product of graphene oxide-phenolsulfonic acid, 93 g of aniline and 868 g of acetone, and reacted at 180 ℃ for 12 h. And after the reaction is finished, removing the water phase and the non-covalent modified product of phenolsulfonic acid of graphene oxide by liquid separation, and then distilling to remove the organic solvent to obtain the product, namely the rubber antioxidant TMQ.
Example 3
Preparation of graphene oxide-based catalyst:
weighing 20 g of graphene oxide, and placing the graphene oxide in 4000 g of ethanol for thorough dispersion by ultrasonic. 20 g of oxalic acid is weighed and dissolved in 200 g of ethanol, and the mixture is added into a graphene oxide system and then stirred for 48 hours. And after modification, washing and centrifuging by using ethanol and deionized water respectively to remove free oxalic acid, and then freeze-drying the product to obtain the oxalic acid non-covalent modified product of the graphene oxide for later use.
Preparing a rubber antioxidant TMQ:
to 500 g of toluene were added 10 g of oxalic acid non-covalently modified product of graphene oxide, 93 g of aniline and 810 g of acetone and reacted at 160 ℃ for 12 h. And after the reaction is finished, removing the water phase and the non-covalent modified product of oxalic acid of graphene oxide by liquid separation, and then distilling to remove the organic solvent to obtain the product of the rubber antioxidant TMQ.
Example 4
Preparation of graphene oxide-based catalyst:
weighing 20 g of graphene oxide, and placing the graphene oxide in 4000 g of dichloromethane for thorough dispersion by ultrasonic waves. 20 g of tartaric acid is weighed, dissolved in 200 g of dichloromethane and added into the graphene oxide system, and then stirred for 48 hours. And after modification, washing and centrifuging by using dichloromethane and deionized water respectively to remove free tartaric acid, and then freeze-drying the product to obtain a tartaric acid non-covalent modified product of graphene oxide for later use.
Preparing a rubber antioxidant TMQ:
to 500 g of toluene were added 10 g of tartaric acid non-covalently modified product of graphene oxide, 93 g of aniline and 928 g of acetone, and reacted at 180 ℃ for 12 h. And after the reaction is finished, removing the water phase and the non-covalent modification product of tartaric acid of graphene oxide by liquid separation, and then distilling to remove the organic solvent to obtain the product, namely the rubber antioxidant TMQ.
Example 5
Preparation of graphene oxide-based catalyst:
weighing 20 g of graphene oxide, and placing the graphene oxide in 4000 g of ethanol for thorough dispersion by ultrasonic. 30 g of citric acid is weighed, dissolved in 200 g of ethanol, added into a graphene oxide system and stirred for 48 hours. And after modification, washing and centrifuging by using ethanol and deionized water respectively to remove free citric acid, and freeze-drying a product to obtain a citric acid non-covalent modified product of graphene oxide for later use.
Preparing a rubber antioxidant TMQ:
to 500 g of toluene were added 10 g of a non-covalently modified product of graphene oxide-p-toluenesulfonic acid, 93 g of aniline and 868 g of acetone, and reacted at 150 ℃ for 16 h. And after the reaction is finished, removing the water phase and the non-covalent modified product of the citric acid of the graphene oxide by liquid separation, and then distilling to remove the organic solvent to obtain the product, namely the rubber antioxidant TMQ.
Example 6
Preparation of graphene oxide-based catalyst:
weighing 20 g of graphene oxide, and placing the graphene oxide in 4000 g of ethanol for thorough dispersion by ultrasonic. 30 g of malic acid is weighed and dissolved in 200 g of ethanol, and added into a graphene oxide system, and then stirred for 48 hours. And after modification, washing and centrifuging by using ethanol and deionized water respectively to remove free malic acid, and then freeze-drying the product to obtain a malic acid non-covalent modified product of graphene oxide for later use.
Preparing a rubber antioxidant TMQ:
to 500 g of toluene were added 10 g of malic acid non-covalently modified product of graphene oxide, 93 g of aniline and 810 g of acetone, and reacted at 160 ℃ for 15 h. And after the reaction is finished, removing the water phase and the non-covalent modified product of the malic acid of the graphene oxide by liquid separation, and then distilling to remove the organic solvent to obtain the product, namely the rubber antioxidant TMQ.
Example 7
Preparation of graphene oxide-based catalyst:
weighing 20 g of graphene oxide, and placing the graphene oxide in 4000 g of ethyl acetate for thorough dispersion by ultrasonic waves. 20 g of lactic acid is weighed and dissolved in 200 g of ethyl acetate, and added into a graphene oxide system, and then stirred for 72 hours. And after modification, washing and centrifuging by using ethyl acetate and deionized water respectively to remove free lactic acid, and then freeze-drying the product to obtain the citric acid non-covalent modified product of the graphene oxide for later use.
Preparing a rubber antioxidant TMQ:
to 500 g of toluene were added 10 g of the non-covalently modified product of graphene oxide-p-toluenesulfonic acid, 93 g of aniline and 868 g of acetone, and reacted at 180 ℃ for 10 h. And after the reaction is finished, removing the water phase and the non-covalent modified product of the lactic acid of the graphene oxide by liquid separation, and then distilling to remove the organic solvent to obtain the product, namely the rubber antioxidant TMQ.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention, such as changing the conversion conditions of the biological system and the reaction material ratio of aniline, etc. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the rubber antioxidant TMQ is characterized in that aniline and acetone are used as raw materials, and the rubber antioxidant TMQ is prepared by catalysis of a graphene oxide-based catalyst in the following form: adding raw materials of aniline, acetone and a graphene oxide-based catalyst into a solvent, mixing and heating to a reaction temperature, and distilling to remove the solvent after reaction to obtain a rubber antioxidant TMQ; the graphene oxide-based catalyst is a non-covalent modified product of graphene oxide and organic protonic acid.
2. The production method according to claim 1, wherein the reaction temperature for producing the rubber antioxidant TMQ is 90 to 180 ℃ and the reaction time is 1 to 20 hours.
3. The method according to claim 1, wherein the weight ratio of aniline to acetone is 1:1 to 10, wherein the weight ratio of the graphene oxide-based catalyst to the aniline is 0.0005 to 0.5:1.
4. the production method according to claim 1, wherein the graphene oxide-based catalyst production method comprises: completely dispersing graphene oxide solid in a solvent, dissolving organic protonic acid in a graphene oxide system, stirring, washing with the solvent and deionized water, and freeze-drying a product to obtain a non-covalent modified product of graphene oxide and organic protonic acid.
5. The method according to claim 4, wherein the solvent is a solvent capable of simultaneously dispersing the graphene oxide completely and dissolving the organic acid compound completely, and is selected from the group consisting of water, methanol, ethanol, methylene dioxide, chloroform, acetone, acetonitrile, ethyl acetate, N, N-dimethylformamide, and dimethylsulfoxide.
6. The method according to claim 4, wherein the dispersion is ultrasonic or stirring dispersion.
7. The process according to claim 4, wherein the organic protonic acid is selected from p-toluenesulfonic acid, benzenesulfonic acid, phenolsulfonic acid, oxalic acid, tartaric acid, citric acid, malic acid and lactic acid.
8. The method of claim 4, wherein the stirring time is 0 to 72 hours.
9. The method according to claim 4, wherein the washing means is centrifugal washing and dialysis.
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| CN101353447A (en) * | 2008-08-27 | 2009-01-28 | 河南省开仑化工有限责任公司 | Synthetic process of rubber antiager RD |
| CN102584696A (en) * | 2012-02-28 | 2012-07-18 | 徐州工业职业技术学院 | Catalytic synthesis method for rubber antioxidant RD |
| CN105017144A (en) * | 2014-04-25 | 2015-11-04 | 江苏圣奥化学科技有限公司 | Rubber aging inhibitor RD and preparation method for same |
| CN106944028A (en) * | 2017-03-21 | 2017-07-14 | 北京化工大学 | A kind of preparation method of the graphene-based complex solid base catalyst of 3D structures |
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| KR101465207B1 (en) * | 2013-10-25 | 2014-11-25 | 성균관대학교산학협력단 | Phase transfer catalyst for organic reactions |
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| CN101353447A (en) * | 2008-08-27 | 2009-01-28 | 河南省开仑化工有限责任公司 | Synthetic process of rubber antiager RD |
| CN102584696A (en) * | 2012-02-28 | 2012-07-18 | 徐州工业职业技术学院 | Catalytic synthesis method for rubber antioxidant RD |
| CN105017144A (en) * | 2014-04-25 | 2015-11-04 | 江苏圣奥化学科技有限公司 | Rubber aging inhibitor RD and preparation method for same |
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